Process for refining hydrocarbon distillate oils with boron fluoride



Patented Get. 18, 1938 UNITED STATES PROCESS FOR DISTILLATE ORIDEREFINING OILS WITH BORON FLU- HYDROCARBON Amiot P. Hewlett, Cranford, N.J., assignor to Standard poration of Delaware No Drawing.

Oil Development Company, a cor- Application December 30, 1933,

. Serial No. 704,765

1 Claim.

This invention relates to the treatment of hydrocarbon oils belonging tothe kerosene, gas oil and lubricating oil ranges with boron fluoride orother halides of similar chemical properties. The

oil tobe treated may be a kerosene distillate or a heavier distillatefrom petroleum. It may be a shale oil boiling within the kerosene rangeor higher. Other oils of similar boiling range produced by lowtemperature carbonization of coal,

in or by hydrogenation of coal, may be treated according to the presentinvention, although the best results are obtained when the invention isapplied to the treatment of petroleum distillates of the boiling rangesspecified. The treating 15 agent is boron fluoride or any of the otherhalides of boron, such as-boron chloride, bromide, iodide, halides oftitanium, such as titanium tetrachloride, and halides of silicon such assilicon fluon'de.

20 One object of the present invention is to remove undesirableconstituents from the distillates submitted to treatment.

Another object is the production of nitrogen bases from the sludgeremoved by the treating 5 agent from certain distillates, especiallythose boiling within the kerosene range.

I have found the halides mentioned above to be very good selectiverefining agents by removing undesirable constituents from the treatedhydro- 30 carbon oil. When burning oils, such as kerosene,

are treated their burning characteristics are improved. The improvementin lubricating oils manifests itself in an increase of gravity and alsoin an improved (increased) viscosity index.

5 The viscosity index is a method of evaluating lubricating oilsdescribed in an article by E. W. Dean and G. H. B. Davis, in vol. 367,No. 10, October, 1929, of Chem. and Met. Engineering. A viscosity indexof 100 designates a good grade 40 Pennsylvania lubricating oil.Kerosenes, lubricating oils or other oils have also a greatly improvedcolor after the treatment.

The treating consists in agitating the hydrocarbon distillate with thetreating agent, settling 5 and separating the sludge. The treating agentmay be added directly to the distillate to be treated, as, for example,by introducing boron fluoride gas into kerosene, or it may be firstdissolved in strong,.say substantially 100% sulfuric acid, and

50 the distillate treated with the sulfuric acid solution of the halide,this last method being especially advantageous when lubricating oils aretreated. After the settling of the sludge, the hydrocarbon distillatemay be filtered in order to 55 eliminate the last traces of sludge and.then washed, neutralized with alkali, and redistilled or finished in anymanner well known to the art.

Boron fluoride and other halides of similar chemical characteristics arealso very effective in refining cycle gas oils from petroleum cracking 5operations for the production of high quality domestic and industrialheating oils. Unrefined cycle gas oils are in many ways unsatisfactoryfor heating purposes inasmuch as they contain certain undesirableconstituents which may become highly corrosive during storage, attackmetal parts of the burner installation and result in clogged screensand. strainers. Certain undesirable constituents of unrefined cycle gasoils also result in the formation of carbonaceous residues on burning.These objectionable characteristics are eliminated by refining the cyclegas oil according to the present invention.

The amount of treating agent used varies with the nature of the treatingagent and also with the oil to be refined. Usually very small quantitiessuch as 0.1-0.4 pound of boron fluoride per barrel of oil givesatisfactory treating results, while much higher quantities such as 1-5lbs. of titanium tetrachloride have to be used for the same degree ofrefinement. The amount of treating agent used may vary within broaderlimits than those just given for illustration.

Certain petroleum and shale oil distillates, especially those boilingwithin the kerosene range, contain nitrogen bases which are valuable inthe manufacture of drugs, special chemicals, dyes and the like. Thesebases can be efiiciently separated by the use of small quantities ofboron fluoride or similar compounds. The distillate is treated as usualwith the boron fluoride or the other agent, and the sludge separated andhydrolyzed in order to liberate the nitrogen bases. Hydrolysis of thesludge may be effected by intimately mixing the sludge with water (hotwater preferred) followed by neutralization with caustic. If preferred acaustic solution may be used instead of water for hydrolysis. The oilcontaining the liberated nitrogen bases may be further treated bydissolving the bases with. an aqueous mineral. acid, separating the acidsolution from the remaining insoluble oil and then adding sodiumhydroxide or other alkali until an alkali reaction results whereby thenitrogen bases are precipitated and can easily be separated from theaqueous solution. 1

The following example will illustrate the present invention: A sample ofheating oil consisting of a cycle stock obtained in cracking gas oil andhaving gravity of 29 A. P. 1., final boiling point 600 F. and color 8Robinson is treated with two What I claim is: 4 ounces per barrel ofboron fluoride. The color An improved process for refining hydrocarbonis improved to 12 Robinson and the total copper distillate oils havinginitial boiling points at least ple given for illustration, but only bythe followboron fluoride and separating the resulting sludge ing claimin which it is my intention to claim all from the oil.

10 novelty inherent in the invention. v AMIOT P. HEWLETT.

